CN116169306B - Fuel cell electrode, method for producing the same, and fuel cell - Google Patents

Fuel cell electrode, method for producing the same, and fuel cell Download PDF

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CN116169306B
CN116169306B CN202310438137.4A CN202310438137A CN116169306B CN 116169306 B CN116169306 B CN 116169306B CN 202310438137 A CN202310438137 A CN 202310438137A CN 116169306 B CN116169306 B CN 116169306B
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layer
fuel cell
growth
boron
substrate
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CN116169306A (en
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易典
王荣福
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Shenzhen Hanyu New Material Technology Co ltd
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Shenzhen Hanyu New Material Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8867—Vapour deposition
    • H01M4/8871—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a fuel cell electrode, a preparation method thereof and a fuel cell. The fuel cell electrode includes: a substrate, a growth base layer, a catalyst layer and a protective layer; the growth basal layer is arranged on the substrate; the catalyst layer is arranged on the growth basal layer, the material of the catalyst layer comprises boron alkene, the material of the growth basal layer comprises metal for catalyzing the growth of the boron alkene, and the boron alkene grows on the growth basal layer; the protective layer is laminated on the catalyst layer, and the material of the protective layer comprises a boron-containing compound. The production cost of the electrode is far lower than that of the traditional technology which needs to adopt platinum metal particles, and the problem that the platinum metal particles are easy to poison and lose efficacy can be well avoided.

Description

Fuel cell electrode, method for producing the same, and fuel cell
Technical Field
The invention relates to the technical field of batteries, in particular to a fuel cell electrode, a preparation method thereof and a fuel cell.
Background
A fuel cell is a device that generates electric energy by chemical reaction of fuel and oxygen, etc. The fuel cell operates on the principle of catalytically reacting fuel and oxygen at electrodes and passing electrons from an external circuit to produce electrical energy. The fuel cell has the advantages of high efficiency, environmental protection, low noise, low emission and the like, and is one of important development directions in the future energy field.
During actual operation of the fuel cell, fuel is passed from the negative side and an electrochemical reaction occurs. In order to promote the progress of the reaction, a catalyst is generally supported on the anode of the fuel cell. Currently catalysts for fuel cells are based on platinum metal particles. However, the cost of the platinum metal particles is too high, and the platinum metal particles are easily influenced by certain impurity gases (such as carbon monoxide) in the actual use process, so that the platinum metal particles are invalid, so that the current fuel cell still has the defects of too high cost, poor stability and the like, which limit the large-scale commercial application of the fuel cell.
Disclosure of Invention
In view of this, in order to improve the stability of use of a fuel cell while reducing the cost thereof, it is necessary to provide a fuel cell electrode, a method for producing the same, and a fuel cell.
According to some embodiments of the present disclosure, there is provided a fuel cell electrode, including: a substrate, a growth base layer, a catalyst layer and a protective layer;
the growth base layer is arranged on the substrate;
the catalyst layer is arranged on the growth basal layer, the material of the catalyst layer comprises boron alkene, the material of the growth basal layer comprises metal for catalyzing the growth of the boron alkene, and the boron alkene grows based on the growth basal layer;
the protective layer is laminated on the catalyst layer, and the material of the protective layer comprises a boron-containing compound.
In some embodiments of the present disclosure, the surface of the borane has a porous structure.
In some embodiments of the present disclosure, the material of the growth substrate layer is selected from one or more of niobium, tantalum, titanium, tungsten, molybdenum, silver, aluminum, and germanium, and the crystal form of the material of the growth substrate layer is a face-centered cubic structure.
In some embodiments of the present disclosure, the material of the protective layer is selected from boron nitride.
In some embodiments of the present disclosure, the growth substrate layer and the catalyst layer grown thereon form a catalytic functional layer disposed between the substrate and the protective layer, and the fuel cell electrode comprises a plurality of catalytic functional layers stacked in sequence.
In some embodiments of the present disclosure, the substrate has two oppositely disposed side surfaces, each of the two side surfaces of the substrate having the growth base layer, the catalyst layer, and the protective layer disposed thereon.
Further, according to some embodiments of the present disclosure, there is also provided a method for manufacturing the fuel cell electrode described in the above embodiments, including the steps of:
preparing the growth base layer on the substrate;
depositing boron atoms on the growth substrate layer by a magnetron sputtering method or a molecular beam epitaxy method to form the boron alkene serving as the catalyst layer;
the boron-containing compound is deposited on the catalyst layer as the protective layer.
In some embodiments of the present disclosure, in the step of forming the boron alkene, boron atoms are deposited on the growth substrate using a magnetron sputtering method to form the boron alkene, and a target material used for the magnetron sputtering method includes a boron target.
In some embodiments of the present disclosure, the temperature within the deposition chamber is controlled to be 300 ℃ to 500 ℃ during the step of forming the borane.
In some embodiments of the present disclosure, in the step of forming the boron alkene, the gas pressure in the deposition chamber is controlled to be 1×10 or less -8 Pa。
In some embodiments of the present disclosure, in the step of forming the borane, the deposition time is controlled to be 20min to 60min.
In some embodiments of the present disclosure, prior to depositing the boron-containing compound on the catalyst layer, further comprising:
the step of preparing the growth substrate layer is repeated one or more times, and the step of preparing the catalyst layer is repeated one or more times, and wherein the growth substrate layer and the catalyst layer are alternately prepared.
Further, according to still further embodiments of the present disclosure, there is also provided a fuel cell including a positive electrode, a negative electrode, and a proton exchange membrane, the positive electrode and the negative electrode being disposed on both sides of the proton exchange membrane, respectively, the negative electrode being the fuel cell electrode according to any of the above embodiments.
The fuel cell electrode provided by the present disclosure includes a growth substrate layer, a catalyst layer, and a protective layer therein. The growth basal layer comprises metal for catalyzing the growth of the borane, the borane is grown on the growth basal layer, the protective layer is arranged on the catalyst layer and comprises a boron-containing compound, and the borane is fixed in the growth basal layer and the protective layer, so that a stable fuel cell electrode structure can be formed.
Compared with the traditional fuel cell electrode, the fuel cell electrode provided by the disclosure adopts the boron alkene as a catalytic component, and can effectively catalyze and convert hydrogen molecules into hydrogen ions. And, by disposing the borane between the growth substrate layer and the protective layer, the catalyst layer including the borane is fixed and protected, and the catalytic performance and the service life of the catalyst layer are ensured. The production cost of the electrode is far lower than that of the traditional technology which needs to adopt platinum metal particles, and the problem that the platinum metal particles are easy to poison and lose efficacy can be well avoided.
Drawings
Fig. 1 shows a schematic structural view of a fuel cell electrode provided by the present disclosure;
FIG. 2 shows a schematic step diagram of a method of manufacturing a fuel cell electrode provided by the present disclosure;
wherein, each reference sign and meaning are as follows:
100. a substrate; 110. growing a basal layer; 120. a catalyst layer; 130. and (3) a protective layer.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items, and "multiple" as used herein includes two or more of the items.
In the present invention, the sum of the parts of the components in the composition may be 100 parts by weight, if not stated to the contrary. Unless otherwise indicated, the percentages (including weight percent) of the present invention are based on the total weight of the composition, and, in addition, "wt%" herein means mass percent and "at%" means atomic percent.
In this context, unless otherwise indicated, the individual reaction steps may or may not be performed in the order herein. For example, other steps may be included between the respective reaction steps, and the order of the reaction steps may be appropriately changed. This can be determined by the skilled person based on routine knowledge and experience. Preferably, the reaction processes herein are performed sequentially.
The present disclosure provides a fuel cell electrode, comprising: a substrate, a growth base layer, a catalyst layer and a protective layer; wherein the growth basal layer is arranged on the substrate; the catalyst layer is arranged on the growth basal layer, the material of the catalyst layer comprises boron alkene, the material of the growth basal layer comprises metal for catalyzing the growth of the boron alkene, and the boron alkene grows on the growth basal layer; the protective layer is arranged on the catalyst layer, and the material of the protective layer comprises a boron-containing compound.
Wherein, the boron alkene refers to a two-dimensional material with a two-dimensional plane structure composed of boron elements. The lattice structure of the two-dimensional material of boron, both theoretically and as actually produced at present, may be more than one, but all should fall within the category of the boranes described herein. Further, in this context, the boranes may also be selected from two-dimensional materials having a cellular lattice structure.
Some current experiments show that the boranes also have the effect of catalytically converting hydrogen molecules into hydrogen ions. In addition, the hydrogen molecules are easily adsorbed on the surface of the boron alkene, so the boron alkene also has better hydrogen storage capacity. However, the related art of applying the boron alkene to the fuel cell has not appeared so far, mainly because how the boron alkene is incorporated into the electrode of the fuel cell remains a relatively difficult problem to solve. On the one hand, the prepared boranes are typically bound to a substrate and are difficult to separate and convert into fuel cell electrodes. On the other hand, the boranes themselves also present higher instability and are relatively easily oxidized, which also limits the application of the boranes to devices.
In order to overcome the problems, the fuel cell electrode provided by the disclosure introduces the metal growth basal layer and the borane into the fuel cell electrode together, the borane is directly prepared on the growth basal layer, so that the problem that the borane is difficult to separate is avoided, and the borane and the metal growth basal layer have good conductivity, so that electrons are conductive to an external circuit. On the basis, a protective layer is introduced on the surface of the catalyst layer, the boron-containing compound can be stably combined with the surface of the prepared boron alkene, and the boron alkene can be stably combined with the growth basal layer. Therefore, the fuel cell electrode including the above-described structure can realize effective use of the boron alkene in the fuel cell electrode.
Compared with the traditional fuel cell electrode, the fuel cell electrode provided by the disclosure adopts the boron alkene as a catalytic component, and can effectively catalyze and convert hydrogen molecules into hydrogen ions. And, by disposing the borane between the growth substrate layer and the protective layer, the catalyst layer including the borane is fixed and protected, and the catalytic performance and the service life of the catalyst layer are ensured. The production cost of the electrode is far lower than that of the traditional technology which needs to adopt platinum metal particles, and the problem that the platinum metal particles are easy to poison and lose efficacy can be well avoided.
In the fuel cell of the present disclosure, the boron alkene may have a structure in which a single layer structure or a plurality of layers of boron atoms are stacked. In addition, the boranes in one catalyst layer may have some lattice distortion or other defects, subject to practical manufacturing considerations. These factors are related to the actual preparation conditions but still fall within the scope of the boranes in the present disclosure.
In the fuel cell of the present disclosure, the bororenes grow on the growth substrate layer, meaning that the bororenes are formed based on the growth substrate layer during the preparation process, which allows for a relatively firm attachment relationship between the bororenes and the growth substrate layer.
Fig. 1 of the present disclosure shows a schematic structural view of a fuel cell electrode of the present disclosure. Referring to fig. 1, the fuel cell electrode includes: a substrate 100, a growth base layer 110, a catalyst layer 120, and a protective layer 130; the growth base layer 110 is disposed on the substrate 100; the catalyst layer 120 is disposed on the growth substrate layer 110, the material of the catalyst layer 120 includes a borane, the material of the growth substrate layer 110 includes a metal for catalyzing the growth of the borane, and the borane grows on the growth substrate layer 110; the protective layer 130 is stacked on the catalyst layer 120, and the material of the protective layer 130 includes a boron-containing compound.
Referring to fig. 1, in some examples of this embodiment, a substrate 100 has opposite side surfaces, and a growth base layer 110, a catalyst layer 120, and a protective layer 130 are provided on both side surfaces of the substrate 100. Wherein the growth base layer 110, the catalyst layer 120, and the protective layer 130 are sequentially stacked in a direction away from the substrate 100. It will be appreciated that in an actual fabrication process, the structures on both side surfaces of the substrate 100 may be fabricated simultaneously to simplify fabrication processes and save fabrication time.
It can be appreciated that by simultaneously providing the growth base layer 110, the catalyst layer 120, and the protective layer 130 on opposite sides of the substrate 100, the loading amount of the borane of the substrate 100 can be increased without substantially additionally increasing the preparation process, thereby increasing the amount of fuel that the fuel cell electrode can temporarily store and the catalytic efficiency.
Referring to fig. 1, in some examples of this embodiment, the growth substrate layer 110 and the catalyst layer 120 grown thereon constitute a catalytic functional layer, which is disposed between the substrate 100 and the protective layer 130, and the fuel cell electrode includes a plurality of catalytic functional layers stacked in sequence.
It will be appreciated that the catalytic functional layer comprises a growth substrate layer 110 and a catalyst layer 120 grown thereon, which is capable of ensuring the growth and stable adhesion of the borene in the catalyst layer 120. However, the boranes present certain thickness or number of layers limitations during actual fabrication, which limit the catalyst loading in the fuel cell electrode. By arranging a plurality of stacked catalytic functional layers, the loading amount of the borane can be further improved, and the amount of fuel which can be temporarily stored and the catalytic efficiency of the fuel cell electrode can be further improved.
Among the plurality of catalytic functional layers, the catalytic functional layer located above has a protective function for the catalytic functional layer located below, and therefore, the protective layer 130 may be laminated on only the catalytic functional layer located outermost.
In the present disclosure, the growth substrate layer 110 is mainly used as a substrate for growing the borane, the growth substrate layer 110 may also be referred to as a catalyst for growing the borane, and the preparation of the borane requires a lattice of materials for the growth substrate layer 110, but in general, the disclosed or undisclosed materials that can be used for growing the borane may be used as the growth substrate layer 110 of the present disclosure, such as metals like silver or aluminum.
In some examples of this embodiment, the surface of the borane in the catalyst layer 120 has a porous structure. The porous structure may be present in the middle or edge portions of the layered structure of the borane. In an actual manufacturing process, the porous structure may be obtained by controlling a specific deposition process. For example, when preparing the boranes by magnetron sputtering, the deposition rate and growth rate of the boron atoms on the growth substrate layer 110 are relatively fast, which is more advantageous for obtaining the boranes having a porous structure, compared to the molecular beam epitaxy. In the fuel cell electrode, by preparing the borane having a pore structure, more gas attachment sites can be provided to improve the loading amount of the fuel gas and the catalytic efficiency.
In some examples of this embodiment, the material of the growth substrate layer 110 may be selected from one or more of niobium, tantalum, titanium, tungsten, molybdenum, silver, aluminum, and germanium. The material can be used as a growth substrate material of the borane and can grow the borane material which can exist stably at room temperature. Further, the crystal form of the material of the growth substrate layer 110 is a face-centered cubic structure. The (111) crystal face in the crystal with the face-centered cubic structure is more matched with the structure of the boron alkene, so that the preparation of the boron alkene with a better lattice structure is more facilitated. Wherein, for part of the metals, the face-centered cubic structure is not the most common structure in nature, but it will be understood that the structure may still be prepared by some reported techniques, and will not be described herein.
In some examples of this embodiment, the material of the growth substrate layer 110 may be selected from one or more of tantalum and tungsten. The bonding force between tantalum and tungsten and the grown borane is significantly higher, which makes the grown borane more difficult to peel from the surfaces of tantalum and tungsten, ensuring the structural stability of the borane in the fuel cell electrode.
In some examples of this embodiment, the material of the protective layer 130 may be selected from boron nitride. The heterojunction can be formed between the boron nitride and the boron alkene, so that the bonding force is stronger, and the boron nitride is a stable material and has a better protection effect.
In this embodiment, the materials of the substrate 100 and the growth base layer 110 may be the same or different. When the material of the substrate 100 and the growth base layer 110 is the same, the substrate 100 and the growth base layer 110 may be integrated, and the surface material of the substrate 100 may be directly used as the growth base layer 110. When the substrate 100 is different from the material of the growth base layer 110, the material of the growth base layer 110 may be prepared on the substrate 100 by, for example, deposition or the like.
In some examples of this embodiment, in the fuel cell electrode, the material of the substrate 100 is selected from one or more of a metallic material and a carbon material to improve the electrical conductivity of the fuel cell electrode as a whole. The material of the substrate 100 may also be selected from other non-conductive but suitable materials for preparing the growth substrate layer 110, such as glass, quartz or silicon.
Further, the present disclosure also provides a method for preparing a fuel cell electrode in the above embodiment, and referring to fig. 2, the method for preparing a fuel cell electrode includes steps S1 to S5, which are specifically as follows.
Step S1, providing a substrate.
In some examples of this embodiment, the material of the substrate 100 may be selected from one or more of a metallic material and a carbon material.
In this embodiment, glass, quartz, or silicon wafer may be selected as the substrate 100 in order to facilitate the growth of subsequent materials.
In this embodiment, the attachment on the surface of the substrate 100 may be removed by ultrasonic cleaning before the growth base layer 110 is prepared. In the ultrasonic cleaning process, ethanol, acetone or isopropanol may be used as an ultrasonic cleaning agent, and then nitrogen is used to blow-dry the surface of the substrate 100, so as to ensure the cleanliness of the nitrogen as much as possible.
And S2, preparing a growth basal layer on the substrate.
In some examples of this embodiment, the manner in which the growth base layer 110 is prepared on the substrate 100 is deposition, such as chemical vapor deposition or physical vapor deposition. In this example, a physical vapor deposition process was selected to prepare the growth substrate layer 110.
In some examples of this embodiment, the manner of preparing the growth base layer 110 on the substrate 100 may be sputtering. For example, in this embodiment, molybdenum metal or tungsten metal may be selected as the growth base layer 110, and then in the actual manufacturing process, a layer of growth base layer 110 may be manufactured on the substrate 100 by means of magnetron sputtering. And, the subsequent preparation of the catalyst layer 120 can be facilitated by controlling the sputtering conditions such that the molybdenum metal or tungsten metal prepared has a lattice of a face-centered cubic structure.
In some examples of this embodiment, the thickness of the prepared growth substrate layer 110 may be controlled to be 1nm to 10nm. For example, the thickness of the prepared growth substrate layer 110 is controlled to be 1nm, 2nm, 4nm, 5nm, 7nm, 10nm. The thickness of the growth substrate layer 110 may also be in a range between the above thicknesses. It will be appreciated that by controlling the deposition rate and deposition time, a film of a desired thickness can be obtained.
In this step, the growth base layer 110 may be simultaneously prepared on opposite side surfaces of the substrate 100 in order to increase the loading amount of the boron alkene in the subsequent step.
And step S3, preparing the boron alkene based on the growth basal layer.
In this embodiment, the boron atoms may be deposited on the growth substrate layer 110 by means of magnetron sputtering or molecular beam epitaxy, and the boron atoms may spontaneously form a borane on the growth substrate layer 110 thanks to the catalysis of the growth substrate layer 110.
In some examples of this embodiment, boron atoms are deposited on the growth substrate by means of magnetron sputtering, the target used in which comprises a boron target. Compared with the molecular beam epitaxy method, the magnetron sputtering method has higher production rate and lower production cost. Although the molecular beam epitaxy method can prepare the boron alkene with more complete crystal lattice, the boron atoms sputtered by the magnetron sputtering method have higher kinetic energy, so that the surface of the formed boron alkene spontaneously has certain morphological defects, thereby being beneficial to obtaining the boron alkene with a porous structure, and being beneficial to the morphology required by the fuel cell electrode.
In some embodiments of the present disclosure, the temperature within the deposition chamber is controlled to be 300 ℃ to 500 ℃ during the step of forming the borane. Further, the temperature in the deposition chamber may be controlled to 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃, 450 ℃ or 500 ℃, and the temperature in the deposition chamber may also be controlled to a range between the above temperatures.
In some examples of this embodiment, the gas pressure in the deposition chamber is controlled to be 1×10 or less during the step of forming the borane -8 Pa。
In some examples of this embodiment, the deposition time may be controlled to be 20 min-60 min during the step of forming the borane. Further, the deposition time may be controlled to be 20min, 22min, 25min, 30min, 40min, 50min or 60min, and the temperature in the deposition chamber may be controlled to be within a range between the above temperatures.
In some examples of this embodiment, in the step of forming the borane, the power of the magnetron sputtering method may be controlled to be 100w to 500w.
In some examples of this embodiment, the thickness of the borane may be controlled to be 0.1nm to 5nm. Further, in some examples of this embodiment, the thickness of the borane may be controlled to be 0.1nm to 3nm.
In some examples of this embodiment, the manner of preparing the catalyst layer 120 and preparing the growth substrate layer 110 is a magnetron sputtering method, and further, the steps of preparing the catalyst layer 120 and preparing the growth substrate layer 110 are performed in the same chamber. This can improve the growth efficiency of the catalyst layer 120 and the growth base layer 110, and can also prevent contamination of the catalyst layer 120 and the growth base layer 110, which may occur during transfer of the substrate 100, and improve the quality of the borane.
In this step, since the substrate 100 has the growth base layer 110 on opposite sides thereof, the catalyst layer 120 may be simultaneously grown on opposite side surfaces of the substrate 100.
And step S4, repeating the step of preparing the growth basal layer for a plurality of times and repeating the step of preparing the catalyst layer for a plurality of times.
In this embodiment, the growth substrate layer 110 that has been prepared and the catalyst layer 120 grown based on this growth substrate layer 110 are taken as a catalytic functional layer as a whole. The purpose of this step is to form further catalytic functional layers stacked one on top of the other.
In some examples of this embodiment, in repeating the step of preparing the growth substrate layer 110 and the step of preparing the catalyst layer 120 a plurality of times, the growth substrate layer 110 and the catalyst layer 120 are alternately prepared. For example, a growth substrate layer 110 is prepared, and then a boron alkene is grown as the catalyst layer 120 based on the growth substrate layer 110; then, a growth base layer 110 is prepared again on the catalyst layer 120 that has been prepared, and a boron alkene is used as the catalyst layer 120 based on the growth base layer 110. After repeated times, a plurality of catalytic functional layers which are sequentially overlapped can be obtained.
In some examples of this embodiment, the later-prepared growth substrate layer 110 may be prepared based on the previously-prepared catalyst layer 120, i.e., the later-prepared growth substrate layer 110 may be in direct contact with the previously-prepared catalyst layer 120. It will be appreciated that the previously prepared catalyst layer 120 has a boron alkene therein which may have the effect of directing the growth of atoms in the subsequently prepared growth substrate layer 110 so as to maintain the crystal lattice of the growth substrate layer 110 and thereby facilitate the subsequent preparation of the catalyst layer 120. In addition, the growth substrate layer 110 is directly prepared based on the catalyst layer 120, which is also helpful to improve the adhesion between adjacent catalytic functional layers, and a more stable structure of the fuel cell electrode is obtained.
In some examples of this embodiment, the number of catalytic functional layers on one of the side surfaces of the substrate 100 may be 50-500 to ensure that the prepared fuel cell electrode has a richer borene.
It will be appreciated that during the actual deposition process, the structure of both sides of the substrate 100 is similar, since both the growth base layer 110 and the catalyst layer 120 may be prepared simultaneously on opposite side surfaces of the substrate 100.
And S5, preparing a protective layer.
In some examples of this embodiment, the material of the protective layer 130 includes a boron-containing compound having a strong bonding force with the borane. The protective layer 130 can block the borane in the catalyst layer 120 from directly contacting the outside on the one hand, and can fix the catalyst layer 120 on the surface layer to prevent gradual peeling.
In this embodiment, the material of the protection layer 130 is boron nitride. Wherein, boron nitride can be prepared on the outermost catalyst layer 120 by deposition, so that the boron alkene in the outermost catalyst layer 120 forms a van der waals heterojunction with the protective layer 130.
In some examples of this embodiment, the manner of preparing the protective layer 130 may also be magnetron sputtering. The steps of preparing the catalyst layer 120 and preparing the protective layer 130 are performed in the same chamber.
In some examples of this embodiment, the thickness of the protective layer 130 may be controlled to be 5nm to 50nm.
It can be appreciated that the fuel cell electrode provided in the present disclosure can be prepared through steps S1 to S5. In the preparation process, the growth basal layer and the borane are jointly introduced into the fuel cell electrode, and the borane is directly prepared on the growth basal layer, so that the problem that the borane is difficult to separate independently can be avoided. On the basis, a protective layer is prepared on the surface of the catalyst layer in a laminated manner. By sequentially preparing the growth basal layer, the catalyst layer and the protective layer, the boracene can be stably fixed on the substrate and protected, and further the fuel cell electrode taking the boracene as a catalyst is realized.
Compared with the traditional fuel cell electrode, the fuel cell electrode provided by the disclosure adopts the boron alkene as a catalytic component, and can effectively catalyze and convert hydrogen molecules into hydrogen ions. And, by disposing the borane between the growth substrate layer and the protective layer, the catalyst layer including the borane is fixed and protected, and the catalytic performance and the service life of the catalyst layer are ensured. The production cost of the electrode is far lower than that of the traditional technology which needs to adopt platinum metal particles, and the problem that the platinum metal particles are easy to poison and lose efficacy can be well avoided.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. A fuel cell electrode, comprising: a substrate, a growth base layer, a catalyst layer and a protective layer;
the growth base layer is arranged on the substrate;
the catalyst layer is arranged on the growth basal layer, the material of the catalyst layer comprises boron alkene, the material of the growth basal layer comprises metal for catalyzing the growth of the boron alkene, and the boron alkene grows based on the growth basal layer;
the protective layer is laminated on the catalyst layer, and the material of the protective layer comprises a boron-containing compound.
2. The fuel cell electrode according to claim 1, wherein the surface of the borane has a porous structure.
3. The fuel cell electrode of claim 1, wherein the material of the growth substrate layer is selected from one or more of niobium, tantalum, titanium, tungsten, molybdenum, silver, aluminum, and germanium, and the material of the growth substrate layer has a face-centered cubic structure in crystalline form; and/or the number of the groups of groups,
the material of the protective layer is selected from boron nitride.
4. A fuel cell electrode according to any one of claims 1 to 3, wherein the growth substrate layer and the catalyst layer grown thereon form a catalytic functional layer, the catalytic functional layer being disposed between the substrate and the protective layer, the fuel cell electrode comprising a plurality of catalytic functional layers stacked in sequence.
5. A fuel cell electrode according to any one of claims 1 to 3, wherein the substrate has opposite side surfaces, and the growth base layer, the catalyst layer and the protective layer are provided on both side surfaces of the substrate.
6. A method of manufacturing a fuel cell electrode according to any one of claims 1 to 5, comprising the steps of:
preparing the growth base layer on the substrate;
depositing boron atoms on the growth substrate layer by a magnetron sputtering method or a molecular beam epitaxy method to form the boron alkene serving as the catalyst layer;
the boron-containing compound is deposited on the catalyst layer as the protective layer.
7. The method of manufacturing a fuel cell electrode according to claim 6, wherein in the step of forming the boron alkene, boron atoms are deposited on the growth substrate layer by a magnetron sputtering method to form the boron alkene, and a target material used for the magnetron sputtering method includes a boron target.
8. The method of manufacturing a fuel cell electrode according to claim 7, wherein in the step of forming the boron ene, the temperature in the deposition chamber is controlled to 300 ℃ to 500 ℃; and/or the number of the groups of groups,
in the step of forming the boron alkene, the air pressure in the deposition chamber is controlled to be less than or equal to 1 multiplied by 10 -8 Pa; and/or the number of the groups of groups,
in the step of forming the boron alkene, the deposition time is controlled to be 20-60 min.
9. The method for producing a fuel cell electrode according to any one of claims 6 to 8, characterized by further comprising, before depositing the boron-containing compound on the catalyst layer:
the step of preparing the growth substrate layer is repeated one or more times, and the step of preparing the catalyst layer is repeated one or more times, and wherein the growth substrate layer and the catalyst layer are alternately prepared.
10. A fuel cell, characterized by comprising a positive electrode, a negative electrode and a proton exchange membrane, wherein the positive electrode and the negative electrode are respectively arranged on two sides of the proton exchange membrane, and the negative electrode is the fuel cell electrode according to any one of claims 1-5.
CN202310438137.4A 2023-04-23 2023-04-23 Fuel cell electrode, method for producing the same, and fuel cell Active CN116169306B (en)

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